U.S. patent number 4,948,879 [Application Number 07/272,781] was granted by the patent office on 1990-08-14 for monoazo compounds containing a fiber-reactive group and an oxazolopyridone or oxazinopyridone coupling component.
This patent grant is currently assigned to Hoechst Aktiengesellschaft. Invention is credited to Dieter Oehme, Werner H. Russ, Horst Tappe.
United States Patent |
4,948,879 |
Tappe , et al. |
August 14, 1990 |
Monoazo compounds containing a fiber-reactive group and an
oxazolopyridone or oxazinopyridone coupling component
Abstract
Monoazo compounds conforming to the general formula (1) shown
and defined hereinafter have very good fiber-reactive dye
properties and dye hydroxy- and/or carboxamido-containing material,
in particular fiber material, such as wool and in particular
cellulose fibers, in strong fast shades. ##STR1## where the symbols
have the following meanings: D is a benzene or naphthalene ring or
a heterocyclic radical, R.sup.1 and R.sup.2 are each independently
of the other hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to
4 carbon atoms, halogen, carboxy or sulfo, Z is a fiber-reactive
grouping bonded to D either directly or via a bridge member, m
stands for the number 1 or 2, preferably 1, R is alkyl of 1 to 4
carbon atoms which may be substituted for example by halogen, such
as bromine and in particular chlorine, hydroxy, cyano, sulfo,
carboxy, sulfato or phosphato, or is phenyl which may be
substituted, for example by 1 or 2 substituents from the group
consisting of methyl, ethyl, methoxy, ethoxy, chlorine, sulfo and
carboxy, or is carboxy, carbamoyl or carbalkoxy of 2 to 5 carbon
atoms, n stands for the number 2 or 3.
Inventors: |
Tappe; Horst (Dietzenbach,
DE), Oehme; Dieter (Florsheim am Main, DE),
Russ; Werner H. (Hofheim am Taunus, DE) |
Assignee: |
Hoechst Aktiengesellschaft
(Frankfurt am Main, DE)
|
Family
ID: |
6340884 |
Appl.
No.: |
07/272,781 |
Filed: |
November 17, 1988 |
Foreign Application Priority Data
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Nov 20, 1987 [DE] |
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3739349 |
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Current U.S.
Class: |
534/642; 534/638;
534/644; 534/582; 534/635; 534/641; 546/116 |
Current CPC
Class: |
C09B
62/0088 (20130101) |
Current International
Class: |
C09B
62/002 (20060101); C09B 62/008 (20060101); C09B
062/028 (); C09B 062/45 (); D06P 001/382 (); D06P
001/384 () |
Field of
Search: |
;534/642,644,635,638,641,617 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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0078024 |
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Sep 1984 |
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EP |
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0181585 |
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May 1986 |
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EP |
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1271226 |
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Apr 1972 |
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GB |
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2010882 |
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Mar 1982 |
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GB |
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Other References
Tilak et al., Chemistry and Industry (London), 29-31,
(1981)..
|
Primary Examiner: Higel; Floyd D.
Assistant Examiner: Powers; Fiona T.
Claims
We claim:
1. A monoazo compound conforming to the formula ##STR19## wherein:
D is a benzene or naphthalene ring or benzothiazol-2-yl,
R.sup.1 and R.sup.2 are each, independently of the other, hydrogen,
alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms,
halogen, carboxy or sulfo,
Z is a group of the formula (2)
in which
X is vinyl, or is ethyl substituted in the .beta.-position by a
substituent eliminable under alkaline conditions to form a vinyl
group, and
A is a direct bond, methylene, ethylene or a group of the formula
(2a) ##STR20## where R* is hydrogen or alkyl or 1 to 4 carbon
atoms, or
Z is .beta.-bromoacryloylamino,
.alpha.,.beta.-dibromopropionylamino,
.beta.-(phenylsulfonyl)propionylamino,
.beta.-(methylsulfonyl)-propionylamino,
.beta.-chloropropionylamino,
2,2,3,3-tetrafluorocyclobutane-1-carbonylamino,
N-(.beta.-sulfatoethylsulfonyl)-N-methyl-or -N-ethyl-amino, or
N-(vinylsulfonyl)-N-methyl-or -N-ethyl-amino or a group of the
formula (3) ##STR21## where R* has the abovementioned meanings,
Y is fluorine or chlorine and
W is fluorine or chlorine or a N-nicotinamide or N-nicotinic acid
group or an amino group of the formula (4) ##STR22## where R.sup.3
is hydrogen, alkyl of 1 to 4 carbon atoms unsubstituted or
substituted by 1 or 2 substituents selected from the group
consisting of sulfo, carboxy, phosphato, sulfato, hydroxy, cyano,
vinylsulfonyl, .beta.-sulfatoethylsulfonyl,
.beta.-chloroethylsulfonyl and phenyl or naphthyl each
unsubstituted or substituted by 1, 2 or 3 substituents selected
from the group consisting of sulfo, carboxy, methyl, ethyl,
methoxy, ethoxy, chlorine, bromine and a group of the formula
--SO.sub.2 --X where X has one of the abovementioned meanings,
or
R.sup.3 is a cycloaliphatic group, and
R.sup.4 is hydrogen or alkyl of 1 to 4 carbon atoms unsubstituted
or substituted by 1 or 2 substituents selected from the group
consisting of sulfo, carboxy, phosphato, sulfato, hydroxy, cyano,
vinylsulfonyl, .beta.-sulfatoethylsulfonyl,
.beta.-chloroethylsulfonyl and phenyl or naphthyl each
unsubstituted or substituted by 1, 2, or 3 substituents selected
from the group consisting of sulfo, carboxy, methyl, ethyl,
methoxy, ethoxy, chlorine, bromine, and a group of the formula
--SO.sub.2 --X where X has one of the abovementioned meanings,
or
R.sup.4 is phenyl or naphthyl each unsubstituted or substituted by
1, 2 or 3 substituents selected from the group consisting of sulfo,
carboxy, chlorine, bromine, methyl, ethyl, methoxy, ethoxy and a
group of the formula --SO.sub.2 --X where X has one of the
abovementioned meanings, or
R.sup.3 and R.sup.4 together with the nitrogen atom form the
piperidino, piperazino or morpholino group, or
Z is a group of the formula (5) ##STR23## where R.sup.5 is
chlorine, fluorine or methylsulfonyl,
R.sup.6 is chlorine, fluorine or methyl and
R.sup.7 is chlorine or cyano
m is the number 1 or 2,
R is hydrogen or alkyl of 1 to 4 carbon atoms unsubstituted or
substituted by halogen, hydroxy, cyano, sulfo, carboxy, sulfato or
phosphato, or is phenyl unsubstituted or substituted by 1 or 2
substituents selected from the group consisting of methyl, ethyl,
methoxy, ethoxy, chlorine, sulfo and carboxy, or is carboxy,
carbamoyl or carbalkoxy of 2 to 5 carbon atoms,
n is the number 2 or 3.
2. A compound as claimed in claim 1, wherein R is alkyl of 1 to 4
carbon atoms.
3. A compound as claimed in claim 1, wherein R is methyl.
4. A compound as claimed in claim 1, wherein m is 1.
5. A compound as claimed in claim 1, wherein n is 3.
6. A compound as claimed in claim 1, wherein R is methyl, n is 3, m
is 1, and Z is a group of the formula X--SO.sub.2 -- wherein X is
vinyl or is an ethyl which is substituted in the .beta.-position by
a substituent eliminable by an alkali.
7. A compound as claimed in claim 1, wherein m is 1 and Z is a
group of the formula X--SO.sub.2 -- wherein X is vinyl or is an
ethyl which is substituted in the .beta.-position by a substituent
eliminable by an alkali.
8. A compound as claimed in claim 1, wherein D is a naphthalene
ring to which the azo group is bonded in the 2-position, R.sup.1
and R.sup.2 have the meanings mentioned in claim 1, m is 1, Z is a
group of the formula X--SO.sub.2 -- wherein X is vinyl or is an
ethyl which is substituted in the .beta.-position by a substituent
eliminable by an alkali, R is methyl and n is 3.
9. A compound as claimed in claim 8, wherein R.sup.1 is hydrogen
and R.sup.2 is hydrogen or sulfo.
10. A compound as claimed in claim 1, wherein D is a benzene ring,
R.sup.1 and R.sup.2 have the meanings mentioned in claim 1, m is 1,
Z is a group of the formula X--SO.sub.2 -- wherein X is vinyl or is
an ethyl which is substituted in the .beta.-position by a
substituent eliminable by an alkali, R is methyl and n is 3.
11. A compound as claimed in claim 6, wherein X is vinyl,
.beta.-thiosulfatoethyl, .beta.-phosphatoethyl, .beta.-chloroethyl
or .beta.-sulfatoethyl.
12. A compound as claimed in claim 7, wherein X is vinyl,
.beta.-thiosulfatoethyl, .beta.-phosphatoethyl, .beta.-chloroethyl
or .beta.-sulfatoethyl.
13. A compound as claimed in claim 8, wherein X is vinyl,
.beta.-thiosulfatoethyl, .beta.-phosphatoethyl, .beta.-chloroethyl
or .beta.-sulfatoethyl.
14. A compound as claimed in claim 10, wherein X is vinyl,
.beta.-thiosulfatoethyl, .beta.-phosphatoethyl, .beta.-chloroethyl
or .beta.-sulfatoethyl.
15. A compound as claimed in claim 1, wherein Z is a group of the
formula X--SO.sub.2 -- wherein X is vinyl or an ethyl group which
is substituted in the .beta.-position by a substituent which is
eliminable by the action of alkali.
16. A compound as claimed in claim 15, wherein X is vinyl,
.beta.-thiosulfatoethyl, .beta.-phosphatoethyl, .beta.-chloroethyl
or .beta.-sulfatoethyl.
17. A compound as claimed in claim 15, wherein X is
.beta.-sulfatoethyl.
Description
DESCRIPTION
The present invention relates to fiber-reactive dyes.
Fiber-reactive water-soluble azo compounds having dye properties
and possessing a 2-hydroxypyridone coupling component have already
been described in the literature, for example in U.S. Pat. No.
4,504,273, in European Patent Applications Nos. 0,080,352A,
0,078,024A and 0,107,614A and in British Patents Nos. 1,271,226 and
2,010,882. The azo dyes described in these publications in terms of
examples are these days considered to have disadvantages for
industrial utilization, whether on account of their molecular
structure, which necessitates an expensive synthesis, or whether on
account of the properties which no longer meet present-day
requirements. Furthermore, fiber-reactive azo compounds having a
2-hydroxypyridone coupling component are known from European Patent
Publication No. 0,181,585A and U.S. Pat. No. 4,659,807.
The present invention now provides novel, useful monoazo compounds
which conform to the general formula (1) ##STR2## where the symbols
have the following meanings: D is a benzene or naphthalene ring or
is a heterocyclic radical, such as a benzothiazol-2-yl radical,
where the substituents Z, R.sup.1 and R.sup.2 are bonded to the
carbocyclic moiety,
R.sup.1 and R.sup.2 are each, independently of the other, hydrogen,
alkyl of 1 to 4 carbon atoms, such as ethyl and in particular
methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and in
particular methoxy, halogen, such as fluorine and in particular
bromine and chlorine, carboxy or sulfo,
Z is a fiber-reactive grouping which is bonded to D either directly
or via a bridge member, such as a substituted or unsubstituted
benzene or naphthalene ring or a substituted or unsubstituted
phenylamino or benzoylamino group or an alkylene group of 1 to 4
carbon atoms,
m stands for the number 1 or 2, preferably 1,
R is an alkyl group of 1 to 4 carbon atoms which may be
substituted, for example by halogen, such as bromine and in
particular chlorine, hydroxy, cyano, sulfo, carboxy, sulfato or
phosphato, or is phenyl which may be substituted, for example by 1
or 2 substituents from the group consisting of methyl, ethyl,
methoxy, ethoxy, chlorine, sulfo and carboxy, or is carboxy,
carbamoyl or carbalkoxy of 2 to 5 carbon atoms, but preferably
alkyl of 1 to 4 carbon atoms,
n stands for the number 2 or 3, preferably 3.
Unsubstituted or substituted alkyl groups R are in particular
methyl and ethyl and also .beta.-chloroethyl, .beta.-hydroxyethyl,
.beta.-cyanoethyl and sulfomethyl.
Fiber-reactive groups Z are those which have been numerously
described in the literature and belong to the reactive radicals not
only of the aliphatic but also of the heterocyclic series. Reactive
radicals of the aliphatic series are in particular those which
derive from groups of the vinyl sulfone series, for example from
groups conforming to the general formula (2)
where
X denotes a vinyl group or is an ethyl group which is substituted
in the .beta.-position by a substituent eliminable under alkaline
conditions to form a vinyl group, for example a .beta.-chloroethyl,
.beta.-acetyloxy, .beta.-thiosulfatoethyl, .beta.-phosphatoethyl
and in particular a .beta.-sulfatoethyl group, and
A is a direct bond or a methylene or ethylene group or an amino
group of the formula (2a) ##STR3## where R* stands for hydrogen or
alkyl of 1 to 4 carbon atoms, such as ethyl and in particular
methyl.
Fiber-reactive groups of the aliphatic series are further for
example .beta.-bromoacryloylamino,
.alpha.,.beta.-dibromopropionylamino,
.beta.-(phenylsulfonyl)propionylamino,
.beta.-(methylsulfonyl)propionylamino, .beta.-chloropropionylamino,
2,2,3,3-tetrafluorocyclobutane-1-carbonylamino,
N-(.beta.-sulfatoethylsulfonyl)-N-methyl-or -N-ethyl-amino and
N-(vinylsulfonyl)-N-methyl-or -N-ethyl-amino.
Fiber-reactive heterocyclic groups are for example those which are
described in German Offenlegungsschrift No. 3,503,746 on pages 9 to
16 and are bonded to D via an amino group of the above formula (2a)
directly or via this amino group and a bridge member. Of these,
particular preference is given to those heterocyclic reactive
radicals which are substituted by halogen, for example
2,6-difluoro-5-chloropyrimidin-4-ylamino,
2-fluoro-5-chloropyrimidin-4-ylamino,
2-fluoro-5-chloro-6-methylpyrimidin-4-ylamino,
2-fluoro-5,6-dichloropyrimidin-4-ylamino and
6-fluoro-2,5-dichloropyrimidin-4-ylamino groups, and in particular
to the halotriazine derivatives conforming to a general formula (3)
##STR4## where R* has the abovementioned meanings,
Y stands for a fluorine or chlorine atom and
W is a fluorine or chlorine atom or denotes a N-nicotinamide or
N-nicotinic acid radical or an amino group of the general formula
(4) ##STR5## where R.sup.3 is a hydrogen atom or an alkyl group of
1 to 4 carbon atoms, such as ethyl or methyl, which may be
substituted, for example by 1 or 2 substituents from the group
consisting of sulfo, carboxy, phosphato, sulfato, hydroxy, cyano,
vinylsulfonyl, .beta.-sulfatoethylsulfonyl,
.beta.-chloroethylsulfonyl or substituted or unsubstituted aryl,
such as phenyl or naphthyl substituted by 1, 2 or 3, preferably 1
or 2, substituents from the group consisting of sulfo, methyl,
ethyl, methoxy, ethoxy, chlorine, bromine, carboxy and a group of
the formula --SO.sub.2 --X where X has one of the abovementioned
meanings, or
R.sup.3 is a cycloaliphatic radical, for example cyclohexyl,
and
R.sup.4 is a hydrogen atom or an alkyl group of 1 to 4 carbon
atoms, such as ethyl or methyl, which may be substituted, for
example by 1 or 2 substituents from the group consisting of sulfo,
carboxyl, phosphato, sulfato, hydroxy, cyano, vinylsulfonyl,
.beta.-sulfatoethylsulfonyl, .beta.-chloroethylsulfonyl or
substituted or unsubstituted aryl, such as phenyl or naphthyl
substituted by 1, 2, or 3, preferably 1 or 2, substituents from the
group consisting of sulfo, methyl, ethyl, methoxy, ethoxy,
chlorine, bromine, carboxy and a group of the formula --SO.sub.2
--X where X has one of the abovementioned meanings, or
R.sup.4 is a substituted or unsubstituted aryl radical, such as
phenyl or naphthyl which may be substituted by 1, 2 or 3,
preferably 1 or 2, substituents from the group consisting of sulfo,
carboxy, chlorine, bromine, methyl, ethyl, methoxy, ethoxy and a
group of the formula --SO.sub.2 --X, where X has one of the
abovementioned meanings, or
R.sup.3 and R.sup.4 together with the nitrogen atom form the
radical of a 5- or 6-membered heterocyclic radical, for example a
piperidino, piperazino or morpholino radical.
Radicals conforming to the general formula (4) are for example
amino, .beta.-(sulfoethyl)amino,
N-methyl-N-(.beta.-sulfoethyl)amino or
N,N-bis-[.beta.-(.beta.'-chloroethylsulfonyl)-ethyl]amino or
phenylamino groups which may each be substituted by 1 or 2
substituents from the group consisting of methyl, ethyl, methoxy,
ethoxy, chlorine, bromine and sulfo and may be additionally
substituted on the N-atom by methyl or ethyl, or a phenylamino
group which may be substituted on the N-atom by methyl or ethyl and
whose phenyl radical is substituted by .beta.-sulfatoethylsulfonyl,
vinylsulfonyl or .beta.-phosphatoethylsulfonyl and may additionally
be substituted by methyl, ethyl, methoxy, ethoxy, chlorine, bromine
or sulfo.
Further preferred fiber-reactive halogen-substituted heterocyclic
radicals Z are those of the general formula (5) ##STR6## where
R.sup.5 stands for chlorine, fluorine or methylsulfonyl,
R.sup.6 is chlorine, fluorine or methyl and
R.sup.7 denotes chlorine or cyano.
Hereinbefore and hereinafter, sulfo groups are groups of the
general formula --SO.sub.3 M, carboxy groups conforming to the
general formula --COOM, sulfato groups are groups conforming to the
general formula --OSO.sub.3 M, thiosulfato groups are groups
conforming to the general formula --S--SO.sub.3 M and phosphato
groups are groups conforming to the general formula --OPO.sub.3
M.sub.2, in each of which M stands for a hydrogen atom or an alkali
metal, such as sodium, potassium and lithium, or for a salt-forming
2- or 3-valent metal.
Of the azo compounds of the general formula (1) according to the
invention, especially commendable ones are those in which R denotes
methyl and n stands for the number 3, further those azo compounds
in which R and n have the abovementioned meanings, in particular
the preferred meanings just mentioned, m stands for the number 1,
and Z denotes a group of the general formula X--SO.sub.2 -- with X
having one of the abovementioned meanings, in particular the
preferred meaning, and D denotes a benzene ring, and also those
conforming to the general formula (1) where R and n have the
abovementioned meanings, in particular the preferred meanings just
mentioned, D is a naphthalene ring to which the azo group is bonded
in the 2-position, m stands for the number 1 or 2, preferably 1,
and Z is a fiber-reactive group of the general formula X--SO.sub.2
-- with X of the abovementioned meanings, in particular the
preferred meaning, and R.sup.1 and R.sup.2 have the abovementioned
meanings, but preferably R.sup.1 being a hydrogen atom and R.sup.2
a hydrogen atom or a sulfo group.
The present invention further provides processes for preparing the
compounds of the general formula (1) according to the invention.
These processes comprise for example coupling the diazonium
compound of an amino compound of the general formula (6) ##STR7##
where Z, m, D, R.sup.1 and R.sup.2 have the abovementioned meaning,
with a compound of the general formula (7) ##STR8## where R and n
have the abovementioned meanings, with simultaneous departure of
the carbamoyl group.
Compounds of the general formula (1) whose fiber-reactive radical Z
is bonded with its amino group --N(R*)-- to D, in particular a
heterocyclic halogen-substituted fiber-reactive radical Z, can
according to the invention also be prepared by reacting an
amino-azo compound of the general formula (8) ##STR9## where D,
R.sup.1, R.sup.2, R, R*, m and n have the abovementioned meanings,
m being particularly preferably 1, with a compound of the general
formula (9)
where Z' is a radical Z of the abovementioned meaning which is free
of the grouping --N(R*)--, and Y.sup.1 stands for a substituent
detachable as an anion, in particular a halogen atom, such as
fluorine or chlorine, in an equivalent amount.
The reaction conditions of the procedures according to the
invention are analogous to known procedures of, on the one hand,
diazotizing and coupling and, on the other, acylating amino
compounds with acylating agents, for example those having reactive
halogen atoms, such as fluorine or chlorine atoms, such as
heterocyclics containing one or two reactive halogen atoms or
compounds having carbonyl chloride or sulfonyl chloride groups. For
instance, the diazotization of the amine of the general formula (6)
to the diazonium salt is carried out in an aqueous medium by means
of a customary nitrosating agent, such as nitrous acid, at a
temperature between -5.degree. C. and +20.degree. C. and at a pH of
2 or less than 2; the coupling reaction can be carried out for
example in an aqueous medium at a temperature between 5.degree. and
25.degree. C. and at a pH between 2 and 8, preferably between 5 and
7. The reaction according to the invention between an aminoazo
compound of the general formula (8) with an acylating agent can be
carried out in an aqueous or in an aqueous-organic medium (the
organic solvent content being a preferably water-soluble solvent
which is inert under the reaction conditions, for example acetone,
dimethylformamide or dimethyl sulfoxide) at a pH between 1 and 8,
preferably between 4 and 6, and at a temperature between
--20.degree. C. and +80.degree. C., preferably between 20.degree.
and 60.degree. C.
The starting compounds of the general formula (8) are easily
preparable analogously to known procedures by coupling the
diazotized amine of the general formula (10) ##STR10## where D,
R.sup.1, R.sup.2, R* and m have the abovementioned meanings, m
being particularly preferably the number 1, with a coupling
component of the abovementioned and above-defined general formula
(7) with departure of the carbamoyl group. The amino compounds of
the general formula (10) are generally known and numerously
described in the literature. Similarly, the starting amino
compounds of the general formula (6) containing the fiber-reactive
radical Z are known or can be prepared analogously to the known
compounds by reacting the corresponding diamino compound of the
general formula (10) of the abovementioned meaning with a compound
of the abovementioned and above-defined general formula (9) in the
manner known and familiar to the person skilled in the art. Such
procedures are described in general terms in the literature or in
patent publications, for example in European Patent Application
Publications Nos. 0,078,009A and 0,212,246A or in the examples of
the abovementioned German Offenlegungsschrift No. 3,503,746.
The coupling component of the general formula (7) with R=methyl and
n=2 which according to the invention serves as a starting compound
is known [see Chem. Ind. (London), 1981, 29-31]. Other starting
compounds of the general formula (7) are preparable analogously to
the process conditions specified therein. For instance, pyridone
compounds of the general formula (13) ##STR11## where R and n have
the abovementioned meaning (which in turn can be prepared as
described in German Offenlegungsschrift No. 3,239,436) are
hydrolyzed at the cyano group in 95-98% strength aqueous sulfuric
acid at a temperature between 50.degree. and 100.degree. C. to
carbamoyl with simultaneous ring formation of the second, fused-on
heterocyclic radical. The compound of the general formula (7)
obtained can subsequently be isolated from the sulfuric acid
solution by precipitation in an ice/water mixture and
filtration.
A process variant for preparing compounds of the general formula
(1) according to the invention where Z stands for a radical of the
general formula (3) and m denotes in particular 1, is associated
with the abovementioned procedure whereby such an azo compound is
prepared by reacting a starting amino-azo compound of the general
formula (8) with a compound of the general formula (9) in which Z'
is a radical of the general formula (11) ##STR12## where W and Y
have the abovementioned meanings. This process variant comprises
reacting--in a manner analogous to known procedures for reacting
dihalotriazine compounds with an amino compound--a compound of the
general formula (12) ##STR13## where R*, R.sup.1, R.sup.2, R, D and
n and also the two Ys have the abovementioned meanings, with an
amino compound of the general formula HNR.sup.3 and R.sup.4 with
R.sup.3 and R.sup.4 of the abovementioned meanings.
The starting compounds of the general formula (12) themselves are
obtained--analogously to the above directions for reacting a
compound (8) with a compound (9)--by reacting a compound of the
general formula (8) with a trihalo-s-triazine, for example cyanuric
fluoride (2,4,6-trifluoro-1,3,5-triazine) or cyanuric chloride
(2,4,6-trichloro-1,3,5-triazine). Such procedures and the reaction
conditions employed for this purpose are numerously described in
the literature (see for example the abovementioned European Patent
Application Publications Nos. 0,078,009A and 0,212,264A). For
instance, the reaction according to the invention to give compounds
of the general formula (1) according to the invention in which Z is
a dihalotriazinylamino radical can preferably be effected at a
temperature between -10.degree. C. and +40.degree. C., preferably
between 0.degree. C. and 30.degree. C., and at a pH between 1.0 and
7.0, preferably between 3.5 and 5, in which case the reaction can
be carried out in an aqueous or aqueousorganic medium of the
abovementioned type. Similarly, the conversion according to the
invention of a compound of the general formula (1) incorporating
the dihalotriazinylamino radical Z into a further compound of the
general formula (1) according to the invention where Z is a radical
of the general formula (3) with W denoting an amino group R.sup.4
R.sup.3 N--can be effected with an amino compound of the general
formula NHR.sup.3 R.sup.4 analogously to the state of the art at a
temperature between 10.degree. and 60.degree. C., preferably
between 20.degree. and 50.degree. C., and at a pH between 2 and 8,
preferably between 5 and 7, and in an aqueous or aqueousorganic
medium of the above-described kind.
Of the coupling components of the general formula (7) used
according to the invention, especially commendable are in
particular those whose radicals in the formula (7) have the
following meanings:
R is methyl and n is the number 3;
R is methyl and n is the number 2;
R is ethyl and n is the number 3;
R is ethyl and n is the number 2;
R is n-propyl and n is the number 3;
R is n-butyl and n is the number 3;
R is phenyl and n is the number 3.
The starting compounds of the general formula (6) used according to
the invention are for example:
4-(.beta.-sulfatoethylsulfonyl)aniline,
2-sulfo-4-(.beta.-sulfatoethylsulfonyl)aniline,
2-chloro-4-(.beta.-sulfatoethylsulfonyl)aniline,
2-bromo-4-(.beta.-sulfatoethylsulfonyl)aniline,
2-methoxy-4-(.beta.-sulfatoethylsulfonyl)aniline,
3-(.beta.-sulfatoethylsulfonyl)aniline,
2-methoxy-5-(.beta.-sulfatoethylsulfonyl)aniline,
2-sulfo-5-(.beta.-sulfatoethylsulfonyl)aniline,
2-chloro-5-(.beta.-sulfatoethylsulfonyl)aniline,
2-bromo-5-(.beta.-sulfatoethylsulfonyl)aniline,
2-sulfo-5-(2',4'-dichloro-s-triazin-6-yl)aminoaniline,
2-sulfo-5-(2'-chloro-4'-amino-s-triazin-6-yl)aminoaniline,
2-sulfo-5-(2'-chloro-4'-methoxy-s-triazin-6-yl)aminoaniline,
2-sulfo-5-[2'-fluoro-4'-(3"-sulfophenyl)amino-s-triazin-6-yl]aminoaniline,
2-sulfo-5-[2'-fluoro-4'-(4"-.beta."-sulfatoethylsulfonyl)amino-s-triazin-6
-yl]aminoaniline,
2-sulfo-5-[2'-chloro-4'-(3"-.beta."-sulfatoethylsulfonyl)amino-s-triazin-6
-yl]amino-aniline,
1-amino-3-N-[3'-(.beta.'-sulfatoethylsulfonyl)phenyl]carboxamide,
6-(.beta.-sulfatoethylsulfonyl)-2-aminonaphthalene,
1-sulfo-6-(.beta.-sulfatoethylsulfonyl)-2-aminonaphthalene,
6-sulfato-8 -(.beta.-sulfatoethylsulfonyl)-2-aminonaphthalene,
8-sulfato-6-(.beta.-sulfatoethylsulfonyl)-2-aminonaphthalene.
The compounds of the general formula (1) prepared according to the
invention can be precipitated or isolated from the synthesis
solutions by generally known methods, for example either by
precipitating from the reaction medium by means of electrolytes,
for example sodium chloride or potassium chloride, or by
evaporating the reaction solution, for example by spray drying, in
which case a buffer substance can be added to this reaction
solution.
The compounds of the general formula (1) according to the
invention--hereinafter referred to as compound (1)--have
fiber-reactive properties and possess very good dye properties.
They can therefore be used for dyeing (including printing) hydroxy
containing and/or carboxamido-containing materials. It is also
possible to use the solutions obtained in the synthesis of
compounds according to the invention, with or without addition of a
buffer substance and with or without concentrating, directly in
dyeing as liquid formulations.
The present invention therefore also provides the use of compounds
(1) for dyeing (including printing) hydroxy-and/or
carboxamido-containing materials, or rather processes for their
application to these substrates. Preferably the materials are
employed in the form of fiber materials, in particular in the form
of textile fibers, such as yarns, wound packages and fabrics. The
procedure adoped here can be analogous to known procedures in that
compound (1) is in dissolved form applied to or incorporated in the
substrate and fixed thereon or therein by heating and/or the action
of an alkaline agent. Hydroxy-containing materials are those of a
natural or synthetic origin, for example cellulose fiber materials
or regenerated products thereof, and polyvinyl alcohols, cellulose
fiber materials being preferably cotton but other vegetable fibers
as well, such as linen, hemp, jute and ramie fibers; regenerated
cellulose fibers are for example staple and filament viscose.
Carboxamido-containing materials are for example synthetic and
natural polyamides and polyurethanes, in particular in the form of
fibers, for example wool and other animal hair, silk, leather,
nylon-6,6, nylon-6, nylon-11 and nylon-4.
Compounds (1) can be applied to and fixed on the substrates
mentioned, in particular on the fiber materials mentioned, by the
application techniques known for water-soluble, in particular for
water-soluble fiber-reactive, dyes. Such dyeing and fixing methods
are numerously described in the literature.
For instance, dyeing cellulose fibers by the exhaust method from a
long liquor using one of a range of acid-binding agents with or
without neutral salts, such as sodium chloride or sodium sulfate,
gives very good color yields and an excellent color buildup. Dyeing
is preferably carried out in an aqueous bath at temperatures
between 40.degree. and 105.degree. C., if appropriate at
temperatures up to 120.degree. C. under pressure, and in the
presence or absence of customary dyeing assistants. A possible
procedure comprises introducing the material into the warm bath and
gradually heating the latter to the desired dyeing temperature and
completing the dyeing process at that temperature. The neutral
salts, which accelerate the exhaustion of the dye, can also be
added to the bath if desired only after the actual dyeing
temperature has been reached.
The padding method likewise produces excellent color yields and a
very good color buildup on cellulose fibers, fixing being possible
by batching at room temperature or elevated temperatures, for
example at up to 60.degree. C., by steaming or by means of dry heat
in a conventional manner.
Similarly, customary printing processes for cellulose fibers, which
can be carried out in a one-step manner, for example by printing
the material with a print paste containing sodium bicarbonate or
another acid-binding agent and compound (1) and by subsequent
steaming at 100.degree. to 103.degree. C., or in a two-step manner,
for example by printing with a neutral or weakly acid print paste
containing compound (1) and subsequent fixing either by passing the
printed material through a hot electrolyte-containing alkaline bath
or by cross-padding with an alkaline, electrolyte-containing
padding liquor and subsequent batching or steaming or dry heat
treatment of this alkali-pretreated material, give strong prints
having well-defined contours and a clear white ground. The outcome
depends only little on varying fixing conditions.
The fixing by means of dry heat in accordance with customary
thermofixing processes is carried out using hot air at 120.degree.
to 200.degree. C. Aside from the customary steam at 100.degree. to
103.degree. C. it is also possible to use superheated steam and
high-pressure steam at temperatures up to 160.degree. C.
The acid-binding agents which bring about a fixation of compounds
(1) on cellulose fibers are for example water-soluble basic salts
of alkali metals and also alkaline earth metals of inorganic or
organic acids or compounds which liberate alkali on heating.
Suitable are in particular alkali metal hydroxides and alkali metal
salts of weak to medium inorganic or organic acids, preferred
alkali metal compounds being the sodium and potassium compounds.
Such acid-binding agents are for example sodium hydroxide,
potassium hydroxide, sodium carbonate, sodium bicarbonate,
potassium carbonate, sodium formate, sodium hydrogenphosphate,
disodium hydrogenphosphate, sodium trichloroacetate, sodium
silicate or trisodium phosphate.
By treating compounds (1) with acid-binding agents, with or without
heating, the former become chemically bonded to the cellulose
fiber; the dyeings thus obtained show excellent wet fastness
properties following the customary aftertreatment by rinsing for
removing unfixed portions of dyes of the formula (1) according to
the invention, in particular since unfixed portions are easy to
wash off on account of their good solubility in cold water.
Dyeings of polyurethane fibers or natural or synthetic polyamide
fibers are customarily carried out in an acid medium. For instance,
the dyebath can be admixed with acetic acid and/or ammonium sulfate
and/or acetic acid and ammonium acetate or sodium acetate in order
to obtain the desired pH. For the purpose of obtaining a dyeing of
usable levelness, it is advisable to add customary leveling
assistants, for example an assistant based on a reaction product of
cyanuric chloride with 3 times the molar amount of an
aminobenzenesulfonic acid and/or an aminonaphthalenesulfonic acid
or based on a reaction product of for example stearylamine with
ethylene oxide. In general, the material to be dyed is introduced
into the bath at a temperature of about 40.degree. C. and agitated
therein for some time, the dyebath is then brought to the desired
weakly acid, preferably weakly acetic acid, pH, and the actual
dyeing is carried out at a temperature between 60.degree. and
98.degree. C. Furthermore, the dyeings can also be carried out at
the boil or at temperatures up to 120.degree. C. (under
pressure).
The dyeings and prints produced using compounds (1) are generally
notable for bright greenish to reddish yellow to yellowish orange
shades and high tinctorial strengths. The dyeings and prints, in
particular those on cellulose fiber materials, have a good light
fastness and good wet fastness properties, for example good wash,
milling, water, seawater, alkaline and acid cross-dyeing and
perspiration fastness properties, and also good fastnesses to
pleating and dry heat setting, hot pressing and crocking.
Also of importance is the use of compounds (1) according to the
invention for the fiber-reactive dyeing of wool. In particular wool
with a non-felting or low-felting finish (cf. for example H. Rath,
Lehrbuch der Textilchemie, Springer-Verlag, 3rd edition (1972),
pages 295-299, in particular the Hercosett finish (page 298); J.
Soc. Dyers and Colourists 1972, 93-99, and 1975, 33-44) is dyeable
to a very high fastness level.
Wool is dyed in a conventional and known manner by subjecting the
fiber-reactive compound (1) to an exhaustion process under pH
control, preferably at the beginning from an acid dyebath at a pH
of about 3.5 to 5.5, and toward the end of the dyeing time shifting
the pH into the neutral or weakly alkaline range up to a pH of 8.5
in order to bring about the full reactive bond between compound (1)
and the fiber, in particular if deep shades are to be obtained. At
the same time, the nonreactively bonded dye portion is dissolved
off.
The procedure described here is also applicable for producing
dyeings on fiber materials made of other natural polyamides or made
of synthetic polyamides and polyurethanes. The dyeings are carried
out at temperatures of 60.degree. to 100.degree. C., but in sealed
dyeing machines they can also be carried out at temperatures of up
to 106.degree. C. Since the water-solubility of compounds (1) is
very good, they are also usable with advantage in customary
continuous dyeing methods. The tinctorial strength of compounds (1)
according to the invention is very high. On fiber materials, in
particular in the reactive dyeing of wool, they produce bright
greenish to reddish yellow to yellowish orange dyeings. On
employing dyeing temperatures of 100.degree. to 106.degree. C. the
exhaustion of the dyebath is found to be high.
In the case of dyeings obtainable with the compounds (1) according
to the invention, it is possible to dispense with an otherwise
customary ammoniacal aftertreatment of the dyed material. Compared
with structurally similar known dyes they surprisingly show a very
good color buildup, the brilliant shade being retained even in very
strong dyeings. Moreover, they are highly compatible with other
fiber-reactive wool dyes which make possible a surprisingly level
dyeing of the fiber. Similarly, material made of wool fibers from
different proveniences can be dyed level with the compounds
according to the invention. To improve the leveling behavior it is
possible, if necessary, to add a customary leveling assistant, for
example N-methyltaurine.
Used in the presence of customary dyeing assistants having an
affinity for wool the compounds according to the invention produce
level dyeings even on wool which has been given a non-felting or
low-felting finish. At pale to medium depths of shade a high wet
fastness level is obtainable even without an ammoniacal
aftertreatment, although in certain circumstances an ammoniacal
aftertreatment can be preferable. Aside from their high light
fastness, these wool dyeings are also notable for good wet fastness
properties, in particular the perspiration fastness properties and
the wash fastness at 60.degree. C., even of dyeings to high depths
of shade.
The Exaples below serve to illustrate the invention. Parts and
percentages are by weight, unless otherwise stated. Parts by weight
bear the same relation to parts by volume as the kilogram to the
liter.
The compounds described below in the Examples in terms of formulae
are shown in the form of the free acids; in general, they are
prepared and isolated in the form of their sodium or potassium
salts and are used for dyeing in the form of their salts. It is
similarly possible to use in the synthesis the starting compounds
and components mentioned in the form of the free acid in the
Examples below, in particular the Table Examples, as such or in the
form of their salts, preferably alkali metal salts, such as sodium
or potassium salts.
The absorption maxima (.lambda..sub.max values) in the visible
region mentioned in the Examples for the azo compounds (1)
according to the invention were determined on the alkali metal
salts thereof in aqueous solution.
EXAMPLE A
88 parts of
1-(.gamma.-methoxy-n-propyl)-2-hydroxy-3-cyano-4-methylpyrid-6-one
(see Example 1 of German Offenlegungsschrift No. 3,239,436) are
stirred without cooling at 25.degree. to 60.degree. C. into 293
parts of 25% strength aqueous sulfuric acid. The reaction mixture
is heated to 80.degree. C., stirred at 80.degree. C. for 2 hours,
cooled down to 25.degree. C. and poured with stirring onto a
mixture of 100 parts of water and 540 parts of ice, this mixture is
brought to pH 6 by means of about 660 parts of a 30 to 33% strength
aqueous sodium hydroxide solution and filtered, and the residue is
dried.
78 parts are obtained of the compound of the formula ##STR14##
bearing the chemical name
8-methyl-6-oxo-3,4-dihydro-2H,6H-pyrido[2,1-b]
[1,3]oxazine-9-carboxamide as a white powder having a melting point
of 229.degree. C.
EXAMPLE B
The coupling component bearing the chemical name
6-carbamoyl-2,3-dihydro-7-methyloxazolo[3,2-a]pyrid-5(4H)-one can
be prepared by the procedure of Example A from
1-(.beta.-methoxyethyl)-2-hydroxy-3-cyano-4-methylpyrid-6-one with
demethylating ring closure and simultaneous hydrolysis of the cyano
group to a carbamoyl group by means of aqueous sulfuric acid (the
2-hydroxypyrid-6-one starting compound itself is obtained by the
method of Example 1 of German Offenlegungsschrift No. 3,239,436,
except that the N-[(.gamma.-methoxy)propyl]cyanoacetamide used
therein is replaced by N-[(.beta.-methoxy)ethyl]cyanoacetamide); it
is obtained as a white powder having a melting point of 238.degree.
C. and has the formula ##STR15##
EXAMPLE 1
29.1 parts of 3-(.beta.-sulfatoethylsulfonyl)aniline are diazotized
in a conventional manner at 0.degree. to 7.degree. C. in an aqueous
hydrochloric acid solution (200 parts of water and 27.6 parts of
31% strength aqueous hydrochloric acid) by stirring into the
solution an aqueous solution containing 7 parts of sodium nitrite.
The solution is then brought to pH 6 with sodium bicarbonate; 20.8
parts of the pyridone compound of Example A are added, and the
coupling is carried out at a pH of 6 to 7 and at a temperature of
15.degree. to 20.degree. C. in the course of 5 hours. The solution
is then admixed with 1 part of kieselguhr and filtered, and the
filtrate is evaporated to dryness.
The monoazo compound according to the invention is obtained as the
sodium salt of the formula ##STR16## in the form of a product
containing electrolyte salt (sodium chloride). It has very good
fiber-reactive dyeing properties and, applied to the materials
mentioned in the description, in particular cellulose fiber
materials, for example cotton, by the application and fixing
methods customary in the art, in particular for fiber-reactive
dyes, produces strong greenish yellow dyeings and prints of good
light fastness and good wet fastness properties, in particular good
wash, milling, cross-dyeing, chlorinated water and perspiration
fastness properties.
EXAMPLE 2
To prepare a monoazo compound according to the invention, the
procedure of Example 1 is followed, except that the diazo component
used in place of the aniline compound used therein is
2-methoxy-5-(.beta.-sulfatoethylsulfonyl)-aniline in an amount of
130.2 parts. The monoazo compound according to the invention of the
formula ##STR17## is obtained as a yellow powder containing
electrolyte salts. The azo compound according to the invention
likewise has very good fiber-reactive dye properties and, applied
by the application and fixing methods customary for fiber-reactive
dyes, produces in particular on cellulose fiber materials, such as
cotton, strong greenish yellow dyeings and prints of good light and
wet fastness properties, such as good wash, milling, cross-dyeing
and perspiration fastness properties.
EXAMPLE 3
To prepare a monoazo component according to the invention, the
procedure of Example 1 is followed, except that the pyridone
coupling component used therein is replaced by the pyridon compound
of Example B used in an amount of 19.4 parts. The monoazo component
according to the invention of the formula ##STR18## is obtained as
a yellow powder containing electrolyte salt. The azo compound
according to the invention likewise has very good fiber-reactive
dye properties and, applied by the application and fixing methods
customary for fiber-reactive dyes, produces in particular on
cellulose fiber material, such as cotton, strong greenish yellow
dyeings and prints of good light and wet fastness properties, such
as good wash, milling, cross-dying and perspiration fastness
properties.
EXAMPLES 4 TO 7
The Table Examples below describe further monoazo compounds of the
general formula (1) according to the invention in terms of their
diazo and coupling components. They are preparable in a manner
according to the invention, for example by the above Working
Examples, by means of the components evident from the particular
Table Example. They possess very good fiber-reactive dye properties
and, applied by the application and fixing methods customary for
fiber-reactive dyes, produce on the materials mentioned in the
description, in particular on cellulose fiber materials, strong
fast dyeings and prints in the hue indicated in the particular
Table Example for dyeings on cotton. The numbers given in brackets
indicate the absorption maximum in nm.
______________________________________ Monoazo compound of the
formula (1) Ex. Diazo component Coupling component Hue
______________________________________ 4 2-methoxy-4-(.beta.- of
Example A yellow sulfatoethylsul- (435) fonyl)aniline 5
6-(.beta.-sulfatoethyl- of Example A yellow sulfonyl)-8-sulfo-
(435) 2-aminonaphthalene 6 2-sulfo-5-(.beta.-sul- of Example A
greenish fatoethylsulfonyl)- yellow aniline (410) 7
4-chloro-3-(.beta.-sul- of Example A greenish fatoethylsulfonyl)-
yellow aniline (416) ______________________________________
APPLICATION EXAMPLE 1
20 parts of the monoazo compound of Example 1 according to the
invention are dissolved in 300 parts of water together with 50
parts of urea. The solution is stirred at below 40.degree. C. into
400 parts of a neutral aqueous 4% strength alginate thickening. 10
parts of sodium carbonate are added, and sufficient 4% strength
aqueous alginate thickening is added to make up to a total amount
of 1000 parts. This is followed by thorough stirring, and the print
paste thus produced is used to print a cotton fabric which, after
drying at 60.degree. C., is treated in a commercially available
steaming unit with saturated steam at 100.degree. to 103.degree. C.
for 5 minutes. The print thus produced is then finished by rinsing
with cold and hot water, washing with a neutral detergent and
further rinsing with water. After the fabric has been dried, it
shows a strong greenish yellow print having the good fastness
properties mentioned in Example 1.
APPLICATION EXAMPLE 2
A fabric made of mercerized cotton is padded with an aqueous dyeing
liquor at 20.degree. C. containing per liter 20 g of the azo
compound of Example 1 according to the invention and 18 g of 33%
strength sodium hydroxide solution to a wet pickup of 70%, based on
the weight of the fabric. The padded fabric is wound onto a
batching roller, wrapped in plastic sheeting and left at room
temperature for 8 hours. It is then finished by rinsing with cold
water, treating with an aqueous bath containing a little acetic
acid and further rinsing in cold and hot water. After drying it
shows a strong greenish yellow dyeing having the good fastness
properties mentioned in Example 1.
APPLICATION EXAMPLE 3
100 parts of a fabric made of mercerized cotton are treated for 10
minutes at 60.degree. C. in 3000 parts of volume of an aqueous
dyebath containing 5 parts of the azo compound of Example 1
according to the invention and 150 parts of anhydrous sodium
sulfate. After this 10-minute treatment, 15 parts of anhydrous
sodium carbonate and 4 parts of 33% strength sodium hydroxide
solution are added, and the dyeing is continued at 60.degree. C.
for 60 minutes. The dyed fabric is then finished in a conventional
manner, for example as in Application Example 2. The result
obtained is a strong greenish yellow dyeing having the good
fastness properties mentioned in Example 1.
APPLICATION EXAMPLE 4
100 parts of a wool fabric are introduced into a hot aqueous
dyebath at 40.degree. C. comprising 3000 parts of water, 2 parts of
the monoazo compound according to the invention described in
Example 1, 0.15 part of an addition product of 12 moles of ethylene
oxide on 1 mole of stearylamine, 2 parts of ammonium acetate and 2
parts of 60% strength aqueous acetic acid. The dyeing temperature
is raised to the boil in the course of 30 minutes, and the dyeing
is then continued at 100.degree. C. for 60 minutes. Following
conventional washing off and finishing this wool fabric shows a
strong greenish yellow shade of very good light fastness and very
good wet fastness properties.
APPLICATION EXAMPLE 5
Application Example 4 is repeated, except that the wool fabric is
replaced by 100 parts of a fabric made of an .xi.-polycaprolactam
fiber, likewise affording a strong greenish yellow dyeing having
good end-use fastness properties.
By following the above Application Examples it is also possible to
use the other monoazo compounds given in the Working and Table
Examples in dyeing and printing, likewise obtaining very strong
dyeings and prints of good light and wet fastness properties in the
hues specified for the respective Working or Table Example.
* * * * *